Intermediate coupling model description of55Fe and57Fe

The properties of the negative parity states of⁵⁵Fe and⁵⁷Fe are investigated in the framework of the intermediate coupling model. In the model, a neutron or a quasineutron is coupled to anharmonic vibrations of the core. Anharmonicities of the vibrations are estimated through the observed properties of the core. Energy levels, spectroscopic factors and electromagnetic properties have been calculated. The results of the present calculations are also compared with available experimental results and other theoretical results. The model reasonably accounts for many of the properties of the low-lying states.     

Spin state and magnetic interaction of cobalt ions in niobium-doped cobaltites

The magnetic properties and electrical conductivity of La_1?x Sr_xCo_1?x/2Nb _x/2O₃ solid solutions with trivalent cobalt ions are studied. These solid solutions are found to be spin glasses with T _f ～ 25 K. The ferromagnetic component is most pronounced in the composition with x = 0.15. The electrical conductivity decreases with increasing strontium content. The results obtained are interpreted within a model according to which cobalt ions located in the vicinity of strontium ions reside in an intermediate-spin state and the Co³⁺-O-Co³⁺ super-exchange interaction is ferromagnetic because of the local dynamic orbital correlations.     

When is a nanoparticle a cluster? An operando EXAFS study of amine borane dehydrocoupling by Rh(4-6) clusters

X-ray absorption fine structure (XAFS) is used to determine the structure of the rhodium cluster present during the catalyzed dehydrocoupling of amine boranes under operando conditions. We show how a variety of XAFS strategies can be used in combination with other analytical methods to differentiate homogeneous from heterogeneous systems. Analysis of the in situ XAFS spectra using a series of amine boranes (NH3BH3, R2NHBH3, and RNH2BH3 where R = methyl, isopropyl, tert-butyl, and cyclohexyl) and rhodium catalyst precursor compounds (including chloro-(1,5-cyclooctadiene)rhodium (I) dimer, bis(1,5-cyclooctadiene)rhodium (I) trifluoromethanesulfonate, chlorodicarbonylrhodium (I) dimer, dichloro(pentamethylcylcopentadienyl)rhodium (III) dimer, hexarhodium hexadecacarbonyl, and tetrarhodium dodecacarbonyl) strongly suggest that the active catalyst species for this reaction is a homogeneous rhodium complex. Rhodium clusters containing four or six rhodium atoms (Rh(4-6)) bound to amine boranes are observed as the major (>99%) rhodium containing species during and after the catalyzed anaerobic dehydrocoupling. During the later stages of the reaction a nonmetallic rhodium complex precipitates in which individual Rh(4-6) clusters likely form polymer chains ligated by the reaction products that have two or more ligating sites. The best fits of the XAFS data, using ab initio calculations of FEFF theory, show that the major rhodium species (80%) has each rhodium atom directly bound to three rhodium atoms with an observed bond distance of 2.73 A and to two boron atoms at 2.10 A. A minor (20%) rhodium species has each rhodium atom bound to four rhodium atoms with a bond distance of about 2.73 A and a single rhodium atom at a nonbonding distance of 3.88 A. No metallic rhodium was observed at any time during the anaerobic reaction.     

Coordination chemistry of H2 and N2 in aqueous solution. Reactivity and mechanistic studies using trans-FeII(P2)2X2)-type complexes (P2 = a chelating, water-solubilizing phosphine)

The reactions of the trans-Fe(DMeOPrPE)2Cl2 complex (I; DMeOPrPE = 1,2-bis(bis(methoxypropyl)phosphino)ethane) and its derivatives were studied in aqueous and nonaqueous solvents with a particular emphasis on the binding and activation of H2 and N2. The results show there are distinct differences in the reaction pathways between aqueous and nonaqueous solvents. In water, I immediately reacts to form trans-Fe(DMeOPrPE)2(H2O)Cl+. Subsequent reaction with H2 or N2 yields trans-Fe(DMeOPrPE)2(X2)Cl+ (X2=H2 or N2). In the case of H2, further reactivity occurs to ultimately give the trans-Fe(DMeOPrPE)2(H2)H+ product (III). The pathway for the reaction I --> III was spectroscopically examined: following the initial loss of chloride and replacement with H2, heterolysis of the H2 ligand occurs to form Fe(DMeOPrPE)2(H)Cl; substitution of the remaining chloride ligand by another H2 molecule then occurs to produce trans-Fe(DMeOPrPE)2(H2)H+. In the absence of H2 or N2, trans-Fe(DMeOPrPE)2(H2O)Cl+ slowly reacts in water to form Fe(DMeOPrPE)32+, II. Experiments showed that this species forms by reaction of free DMeOPrPE ligand with trans-Fe(DMeOPrPE)2(H2O)Cl+, where the free DMeOPrPE ligand comes from dissociation from the trans-Fe(DMeOPrPE)2(H2O)Cl+ complex. In nonaqueous solvents, the chloride ligand in I is not labile, and a reaction with H2 only occurs if a chloride abstracting reagent is present. Complex III is a useful synthon for the formation of other water-soluble metal hydrides. For example, the trans-[Fe(DMeOPrPE)2H(N2)]+ complex was generated in H2O by substitution of N2 for the H2 ligand in III. The trans-Fe(DHBuPE)2HCl complex (DHBuPE = 1,2-bis(bis(hydroxybutyl)phosphino)ethane, another water-solubilizing phosphine) was shown to be a viable absorbent for the separation of N2 from CH4 in a pressure swing scheme. X-ray crystallographic analysis of II is the first crystal structure report of a homoleptic tris chelate of FeII containing bidentate phosphine ligands. The structure reveals severe steric crowding at the Fe center.     

Origin of grey spots on the surface of metallic glasses under Ar ion irradiation: The surface and volume properties

The nature of grey spots on the surface of amorphous Fe₆₇Cr₁₈B₁₅ metglass ribbons irradiated by 30 keV Ar⁺ ions is investigated. Changes in the surface and volume properties of samples are analyzed bearing in mind the presence of competitive processes of ordering and disordering in the structure under irradiation at initial stage of crystallization (T = 500 °C). Changes in the volume properties of the samples become apparent in their structure, electrical and magnetic properties and are caused by radiation-enhanced diffusion at high gradients in the concentration of defects generated by Ar⁺ irradiation. It is established that grey spots are shown by decrease in the reflection coefficient in a visible range. They emerge as a result of reorganization in the electronic structure of irradiated ribbons due to damage in the short-range order and formation of non-uniformly scaled atomic structure during transition from the medium-range to the long-range atomic order. Experimental data are in accord with the calculations in the framework of the free electrons model.     

From almost zero magnetostriction to giant magnetostrictive effects: recent results

A selected review of recent magnetostrictive material investigations is presented. Particular attention is paid to the artificially structured solids-like nanoscale magnetic multilayers and nanosize magnetic alloys. Topics covered also include the magnetoelastic effects in manganates, cobaltates and high-temperature superconductors.     

Local observation of reverse-domain superconductivity in a superconductor-ferromagnet hybrid

Nanoscale magnetic and superconducting properties of the superconductor-ferromagnet Nb/PbFe12O19 hybrid were studied as a function of applied magnetic fields. Low-temperature scanning laser microscopy (LTSLM) together with transport measurements were carried out in order to reveal local variations of superconductivity induced by the magnetic field template produced by the ferromagnetic substrate. Room temperature magnetic force microscopy (MFM) was performed and magnetization curves were taken at room and low temperature to investigate the magnetic properties of the hybrid. Comparative analysis of the LTSLM and the MFM images has convincingly demonstrated the presence of the reverse-domain superconductivity.     

Detection of hydrogen bonding in solution: a 2H nuclear magnetic resonance method based on rotational motion of a donor/acceptor complex

The effect of hydrogen bonding on the rotational correlation time of an H-bond acceptor, pyridine N-oxide-d(5), in various solvents was investigated using the (2)H spin-lattice relaxation time (T(1)). The results demonstrate a linear relationship between viscosity and measured rotational correlation times, an example of Stokes-Einstein-Debye behavior. The results also clearly demonstrate reduced rotational rates for the probe in hydrogen bonding solvents in comparison to solvents incapable of forming hydrogen bonds with the probe. The utility of this observation was exploited to estimate the association constant (K(a)) through an NMR titration procedure. These results are presented as a new technique that can be applied to the characterization of hydrogen bonding in similar systems.     

Thermal stability of A-site ordered PrBaMn2O6 manganites

The crystal structure and electromagnetic properties as well as thermal stability of the A-site ordered PrBaMn₂O₆ manganites have been investigated. These samples have been prepared by using ‘two-steps’ synthesis mode. They have tetragonal structure with no tilt of MnO₆ octahedra and show ferromagnetic metal to paramagnetic semiconductor transition. The most significant structural feature of the A-site ordered manganites is that the MnO₂ sublattice is sandwiched by two types of rock-salt layers PrO and BaO. The different degree of Pr and Ba ions in the A-sublattice is revealed. The A-site ordered PrBaMn₂O₆ sample with maximum degree of the A-site order demonstrates ferromagnetic metallic to paramagnetic insulating transition with the Curie point ∼320 K. The A-site disordered Pr_0.50Ba_0.50MnO₃ sample is ferromagnetic metal below T_C≈140 K. The cation order in these compounds is stable in air up to 1300 °C. For the partly A-site ordered samples the magnetic and electronic phase separation is observed. The magnetotransport properties of the A-site ordered manganites treated under different conditions are discussed in terms of the superexchange interactions and A-site order degree.     

Magnetic, resonance and transport properties of nanopowder of La0.7Sr0.3MnO3 manganites

X-ray powder diffraction, magnetization, transport and magnetic resonance measurements of nanosize La_0.7Sr_0.3MnO₃ (LCMO) manganites have been performed. The nanosize manganites were synthesized with a co-precipitation method at different (600, 700, 800 and 1000 °C) temperatures. The crystal structure of the nanopowders obtained was determined to be perovskite-like with a rhombohedral distortion (the space group R3¯c). The average size of synthesized nanoparticles (from 17 to 88 nm) was estimated using the X-ray diffraction and low temperature adsorption of argon methods. All the nanosize manganites show ferromagnetic-like ordering. Both the Curie temperature and magnetization decrease with reducing the particle size. The decrease of magnetization is due to the disordered surface shell of particles. The disordered surface layer is a source of the surface anisotropy and is responsible for the increase of coercivity. Temperature dependences of the magnetic resonance spectra parameters have allowed obtaining information on dynamics of magnetic properties in the nanoparticle systems. The resistivity was established to become higher by reducing the particles’ size and increases to a great extent in nanoparticles with the smallest average size at low temperatures. The magnetic entropy was shown to be smaller for the small particles. Using the temperature dependence of magnetic entropy the relative cooling power of the nanosize samples studied was evaluated.